Substituted O-(aminosulfonyl)-glycolic anilides

ABSTRACT

New and valuable substituted O-(aminosulfonyl)-glycolic anilides and a process for controlling the growth of unwanted plants with these compounds.

United States Patent [191 Fischer et al.

[73] Assignee: Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine). Germany {22] Filed: Sept. 3, 1974 [21] Appl. No.: 502.742

Related US. Application Data [63] Continuation of Ser. No, 321.548. Jun. 5. 1973. Put.

[30] Foreign Application Priority Data Jan. I3 1973 Germany 220N132 [451 Nov. 11, 1975 [52] US. Cl 260/456 A [5]] Int. Cl. C07C 143/02 [58] Field of Search 260/456 A; 7l/l03 [56] References Cited UNITED STATES PATENTS 3.536.721 l0/l970 Soong et al. 260/456 A Primary E.\'mninerHoward T. Mars Assistant E.rmniner-Nick v Chan Attorney, Agenr, or Firm-Johnston, Keil, Thompson & Shurtleff [57] ABSTRACT New and valuable substituted O-[uminosulfonyliglycolic anilides and a process for controlling the growth of unwanted plants with these compounds.

42 Claims, No Drawings 1 II R NHS0 OCH C N where R denotes hydrogen. alkyl. haloalkyl or cycloalkyl. R denotes phenyl and R" denotes alkyl. alkenyl, alkynyl. cycloalkyl or benzyl, have a good herbicidal action.

R may be. inter alia. methyl. ethyl. propyl. isopropyl, butyl. isobutyl, sec-butyl, pentyl. cyclopentyl, hexyl. cyclohexyl. 2-chloroethyl.

R may be. inter alia. methyl, ethyl. propyl. isopropyl, n butyl. isobutyl. sec-butyl. tert-butyl. pentyl. cyclopentyl. hexyl, cyclohexyl. ally], butenyl. pentenyl. hexenyl. propargyl. butynyl. pentynyl. hexynyl. benzyl.

The herbicidal action of the new compounds is particularly in evidence on the following weeds:

slender fouail amaranth species wild oat brome species goosefoot species [)m-rylis glunu'rulu orchardgrass Digimriu .muguiuulis large crahgrass L'rliium'hfua crm gulli barnyardgrass Elvminv indict! goosegrass catchweed bedstraw deadnettle species ryegrass species chamomile panicum spp. bluegrass species .Scmriu s ip. foxtail species Siuupis urn'm'is wild mustard without causing damage to the crop plants:

Allium (c/u! onions 8cm rulgurix beet Bruxsim s ap. cabbage species ('ucmnis .\'uli\llS cucumbers Dam-m carom carrots Gmxypium hiliunum cotton Ht'lirmllms umluux sunflower Hunk-um vulgurc barley Luclm'u SP1). lettuce species Linum n.\'imti.t.siu|um flax t'llcdicugu .mI/ru alfalfa ()rym .iulii'u rice lclrmclinmn .mriru/n parsley Piximl .mu'l um peas P/mwvulm .rp J. beans Svju hixpiz/u lG/ycim' 1mm.) so beans .Yulmuml mhvmmm potatoes Spinm'iu ulvrucm spinach Surglunn hiculur sorghum Irilicum umlirum wheat I'rlfulimn .rpp. clover Zcu lrmys Indian corn Application rates are from 0.2 to kg of active ingredient per hectare; the compounds may be applied before sowing. or before or after emergence of the plants.

The compounds of the invention may be prepared by reacting a substituted glycolic anilide with a substituted aminosulfonyl chloride in the presence of an acid acceptor, e.g.. triethylamine and pyridine.

EXAMPLE 1 0- isopropylaminosulfonyl l-glycolic acid-N-butyn-1-yl-3-anilide At 0 to 5C and while stirring. a solution of 333 parts by weight of isopropylaminosulfonyl chloride in parts by weight of dichloromethane was added to a solution of 35.5 parts by weight of glycolic acid-N-butynl-yl-3-anilide and 21.4 parts by weight of triethylamine in 600 parts by weight of dichloromethane. After 2 hours the reaction mixture was successively washed with dilute hydrochloric acid. water. sodium bicarbonate solution. and again with water. and then dried with magnesium sulfate. The crude product. melting at 99 to C was obtained from the organic phase upon concentration in vacuo. The pure compound melting at 108 to 1 10C may be obtained by recrystallization from benzene.

The compound has the following structural formula:

seam-s0 OCH2-C-N on J CH-CH t 3 c "I ca The compounds listed below may be obtained analogously:

o '1 n miso oca cu Glycolic acid-N-methylanilide A solution of 10.7 parts by weight of N-methylaniline in 20 parts by weight of tetrahydrofuran has added to it. at to C and with stirring. a solution of 10.2 parts by weight of l.3-dioxo1ane-2.4-dione in parts by weight of tetrahydrofuran. The reaction mixture was then stirred at room temperature until no more carbon dioxide evolved. and subsequently concentrated to dryness in vacuo. The crude product obtained melts at 48 to 50C the analytically pure compound is obtained by recrystallization from ether; m.p.: 50 to 52C.

The following compounds were obtained analogously:

glycolic aeid-N-ethylanilide. m.p. 39 to 41C glycolic acid-N-n-propylanilide. m.p. 68 to 69C glycolic acid-N-propargylanilide. m.p. 69 to 71C glycolic acid-N-3-methylbutynl yl3-anilide glycolic acid-N-allylanilide glycolic acid-N-butenl -yl-3-anilide glycolic acid-N-3-methylbuten- 1-yl-3-anilide glycolic acid-N-cyclohexylanilide glycolic acid-N-cyclopentylanilide glycolic acid-N-benzylanilide.

The agents according to the invention may be used as solutions. emulsions. suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct. hydrocarbons having boiling points higher than 150C, c.g. tetrahydronaphthalene or alkylated naphthalenes. or organic liquids having boiling points higher than 150C and having one or more than one functional group, e.g. the keto group. the ether group. the ester group or the amide group, this group or these groups being attached as substituent(s) to a hydrocarbon chain or being a component of a heterocyclic ring. may be used as spray liquids.

Aqueous formulations may be prepared from emulsion concentrates. pastes or wettable powders by adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents. e.g.. polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be prepared from active ingredient. emulsifying or dispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier. e.g.. kieselguhr. talc. clay or fertilizers.

Granules may be prepared by applying the active ingredients to solid carriers of various particle sizesv Adherents, oils and other herbicidal active ingredients may also be added.

EXAMPLE 2 In the greenhouse. loamy sandy soil was filled into pots and sown with Zen muvv. Sofa hispida. Gossypium llirsulum, Bela vu/guris. Ec/iiimt'hhm t'rus-gulli. Scmria .vpp.. Pou trivia/ix. Bromus Iec'wrum and Alnpec'urus nrvusm'm'des. The soil prepared in this manner was then treated with 2 kg per hectare of 0-(isopropylaminosulfonyl)-glycolic acid-N-butyn-l-yl-3-anilide (1) and. for

comparison. with 2 kg per hectare of chloroacetic acid- N-isopropylanilide (11). each active ingredient being dispersed in 500 liters of water per hectare.

After 4 to 5 weeks it was ascertained that active ingredient 1 had the same good crop plant compatibility as ll, combined with a stronger herbicidal action.

The results of this experiment are given below:

Active ingredient 1 ll Zea may 0 Snju lliipiilu Ben: ulyuris (l 100 complete destruction EXAMPLE 3 Aeti\ e ingredient (J no damage 1()(] complete destruction The action of the following compounds corresponds to that of 1 above:

0-( isopropylaminosulfonyl )-glycolie acid-N- methylanilide 0-isopropylaminosulfonyl )-glycolic acid-N- isobutylanilide O-( ethylaminosulfonyl )-glycolic acid-N-butynl -yl-3- anilide O-(isopropylaminosulfonyl )-glycolic acid-N-butylanilide EXAMPLE 4 90 parts by weight of compound 1 is mixed with 10 parts by weight of N-methyLa-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 5 20 parts by weight of compound I is dissolved in a mixture consisting of parts by weight of xylene. l0

parts by weight of the adduct of 8 to 10 moles of ethylene oxide to l mole of oleic acid-N-monoethanolamide. parts by weight of the calcium salt of dodecylbenzenesulfonic acid. and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of caster oil. By pouring the solution into l00.000 parts by weight of water and uniformly distributing it therein. an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 6 20 parts by weight of compound I is dissolved in a mixture consisting of 40 parts by weight of cyclohexa none. 30 parts by weight of isobutanol. 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol. and parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of caster oil. By pouring the solution into l00,000 parts by weight of water and uniformly distributing it therein. an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 7 parts by weight of compound I is dissolved in a mixture consisting of parts by weight of cyclohcxanol. 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C. and l0 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into l00.000 parts by weight of water and uniformly distributing it therein. an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 8 20 parts by weight of compound I is well mixed with 3 parts by weight of the sodium salt of diisobutylnapthztlene-a-sulfonic acid. l7 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulflte EXAMPLE 10 30 parts by weight of compound I is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE ll Loamy sandy soil was filled into pots and sown with Soju lrispidu. (ioxvvpimn llirs'ulum. Hem lulgm'is. Brussit'u mipux, l'lellunrlms (HHlllllS. Pismrl .Stlllllllll. Allium cepu. Spinut'iu u/cmc'cu. licliinoc'lilou truss-guilt. Digimriu .rzmguinal/is. Semi-in fuberfi Pun umiuu. Lolium Iilliltif/(M'li/H. lilcnsine India: and Malricurz'u chumo mil/u. The soil prepared in this manner was immediately treated with 2 kg per hectare of each of the following active ingredients:

V acid-N- Vll 0-(isopropylaminosulfonylJ-glycolic acidN- ethylanilide Vlll 0-(ethylaminosulfonyl )-glycolic acid-N- ethylanilide After 3 weeks it was ascertained that the active ingredients exhibited good crop plant compatibility combined with an excellent herbicidal action.

The results are given below:

Actiu: ingredient I ll] l\ \l V" \lll Crop plants: Suja his u'dn 0 5 ll 0 0 0 l) (imxypimn llirmmm 0 l) (I 0 (I t) 0 ('HI \uLeurix (I I) 0 0 0 0 0 Emu/(1| nupm 0 ll ll 0 l) (I 0 Helium/1m llIUHllM ll 0 0 0 ll 0 ll Allium u'pu ll 0 0 0 0 0 ll Spinach: uh'ruu'u l) 0 0 0 0 0 0 lisum .mlivum t) (I ll 0 (I I) 0 L n anted plants: lithium-Mun rrmwulli )5 ltltl )5 95 l00 I00 95 [)iglmriu .mngm'milis )5 I00 95 100 )5 90 .Srmriu juhl'rii )5 I00 J0 I00 95 95 Iun ummu I00 I00 100 l0t| 100 )5 [.nlium mnllljlm'mn I00 100 )5 95 I00 Hill 95 Iilvmim' imlim I00 W0 95 )0 I00 95 90 .Wulriulriu ('Illlllllllllifll! X0 90 X0 80 JU till 75 1) no damage I00 complete destruction waste liquor, and 60 parts by weight of powdered silica EXAMPLE 12 gel. and triturated in a hammer mill. By uniformly distributing the mixture in 20.000 parts by weight of water. a spray liquid is obtained containing 0. W1 by weight of the active ingredient.

EXAMPLE 9 3 parts by weight of compound I is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

9 III (I-( propylaminosu lfonyl l-glycolie acid-N-butynl-yl-3-anilide IV (I-(isopropylaminosulfonyll-glycolic acid-N-hutcnl-yl-3-anilide (I-( isopropylaminosulfonyl l-glycolic methylanilide VI (HmethylaminosultonylI-glycolic acid-N-hupvnl- \'l-3-anilidc V acid-N- Vll (H isopropylaminosulfon l I-glycolic acid-N- ethylanilide VIII U-(ethylaminosultonylJ-glycolic acid-N ethylanilidc.

hon atoms. R denotes phenyl. and R denotes alkyl of one to six carbon atoms.

2. The compound of claim I which is U-(aminosulfonyl )-gl \'colic acid-N-isoprop 'lanilide.

3. The compound of claim I which is (I-(meth \'laminosullom'l I-glycolic acid-N-isoproptlanilide. 4. The compound of claim I which is (ethylaminosultonyl J-glycolic acid-N-isopropylanilide.

5. The compound of claim I which is propylaminosullonyl )-gl \'colic acid-N-isopropylanilide.

6. The compound of claim I which is (I-(isopropylaminosull'onyl I-glycolic acid-N-isopropylanilide.

After 3 weeks it was ascertained that the active ingredients exhibited l'avorahle crop plant compatihilit combined with a good herbicidal action.

The results are given below:

7. The compound of claim I which is (I-(n butylaminosultonyl glycolic acid-N-isopropylanilide.

8. The compound of claim I which is (Hsechutylaminosulfonyl I-glycolic acid-N-isopropy Ianilide.

Aetiw ingredient I III I\' \'I \II \'III ('rop plants )niu [in villa (I ti lJ ll II 5 (I Belt! Ill/gun's (I II ll I) (I II (I (Jinn 1mm hll'mmm (I II II I) (I II (I than: \oll'm It) 5 5 l5 5 Ill 5 Int/111mucvitum III 5 5 5 i 5 III 5 1m IIIII\\ 0 II n o o 5 o Inuanted plants.

ll no damage lIIU 1 complete destruction 35 9. The compound of claim I which is (I-aminosul fonyl )-glycolic acid-N-tert-butylanilide.

I0. The compound of claim I which is (I-(mc- The action of the following compounds corresponds to that of the compounds examined in Examples 1 l and acid-Ntertacid-Nmethylaniacid-N-nacid-N-n II R I R NHSOQOCHECN R where R' denotes hydrogen or alkyl of one to six carthylaminosulfonyl I-glycolic acid-N-tert-hutylanilide.

II. The compound of claim I which is t)- (ethylaminosulfonyl)-glycolic acid-N-tert-butylanilide.

I2. The compound of claim I which is (I-(npropylaminosulfonyl )-glycolic acid-N-tcrtbutylanilide.

I3. The compound of claim I which is (I-(isopropylaminosulfonyl I-glycolic acid-N-tertbutylanilide.

I4. The compound of claim 1 which is (J-(n butylaminosulfonyl I-glycolic acid-N-tert-butylanilide.

15. The compound of claim I which is O-(secbutylaminosulfonyl )-glycolic acid-N-tertbutylanilide.

16. The compound of claim 1 which is (I-(aminosulfonyl )-glycolic acid-N-methylanilide.

17. The compound of claim I which is U-(methylaminosulfonyl)-glycolic acid-N-methylanilide.

18. The compound of claim I which is U- (ethylaminosulfonyl )-glycolic acid-N-methylanilide.

19. The compound of claim I which is ()-(npropylaminosulfonyl I-glycolic acid-N-methylanilide.

20. The compound of claim I which is (Hisopropylaminosulfonyl l-glycolic acid-N-methylanilide. 21. The compound of claim I which is (butylaminosulfonyl l-glycolic acid-N-methylanilide.

22. The compound of claim I which is 0-(sechutylaminosulfonyl)-glyc0lic acid-N-methylanilide.

23. The compound of claim I which is 0-(aminosulfonyl )-glycolic acid-N-e thylanilide.

24. The compound of claim 1 which is ()-(methylaminosulfonyl )-gl vcolic acid-N-ethylanilide.

25. The compound of claim I which is O- (ethylaminosulfonyl )-glycolic acid-N-ethylanilide.

26. The compound of claim 1 which is O-(npropylaminosulfonyl )-glycolic acid-N-ethylanilide.

27. The compound of claim l which is (J-(isopropylaminosulfonyl l-glycolic acid-N-ethylanilide.

28. The compound of claim I which is O-(aminosulfonyl l-glycolic acid-N-propylanilide.

29. The compound of claim 1 which is (]-(methylaminosulfonyl )-glycolic acid-N-n-propylanilide.

30. The compound of claim 1 which is (cthylaminosulfonyl )-glycolic acid-Nm-propylanilide.

3]. The compound of claim 1 which is 0 (n propylaminosulfonyl )-gl vcolic acid-N-n-propylanilide.

32. The compound of claim 1 which is O-(isopropylaminosulfonyl )-glycolic acid-N-n-propylanilide.

33. The compound of claim 1 which is O-(aminosulfonyl )-glycolic acid-N-sec-butylanilide.

34. The compound of claim 1 which is O-(me- 

1. A SUBSTITUTED 0-(AMINISULFONYL)- GLYCOLIC OF THE FORMULA
 2. The compound of claim 1 which is 0-(aminosulfonyl)-glycolic acid-N-isopropylanilide.
 3. The compound of claim 1 which is 0-(methylaminosulfonyl)-glycolic acid-N-isopropylanilide.
 4. The compound of claim 1 which is 0-(ethylaminosulfonyl)-glycolic acid-N-isopropylanilide.
 5. The compound of claim 1 which is 0-(n-propylaminosulfonyl)-glycolic acid-N-isopropylanilide.
 6. The compound of claim 1 which is 0-(isopropylaminosulfonyl)-glycolic acid-N-isopropylanilide.
 7. The compound of claim 1 which is 0-(n-butylaminosulfonyl)-glycolic acid-N-isopropylanilide.
 8. The compound of claim 1 which is 0-(sec-butylaminosulfonyl)-glycolic acid-N-isopropylanilide.
 9. The compound of claim 1 which is 0-aminosulfonyl)-glycolic acid-N-tert-butylanilide.
 10. The compound of claim 1 which is 0-(methylaminosulfonyl)-glycolic acid-N-tert-butylanilide.
 11. The compound of claim 1 which is 0-(ethylaminosulfonyl)-glycolic acid-N-teRt-butylanilide.
 12. The compound of claim 1 which is 0-(n-propylaminosulfonyl)-glycolic acid-N-tertbutylanilide.
 13. The compound of claim 1 which is 0-(isopropylaminosulfonyl)-glycolic acid-N-tertbutylanilide.
 14. The compound of claim 1 which is 0-(n-butylaminosulfonyl)-glycolic acid-N-tert-butylanilide.
 15. The compound of claim 1 which is 0-(sec-butylaminosulfonyl)-glycolic acid-N-tertbutylanilide.
 16. The compound of claim 1 which is 0-(aminosulfonyl)-glycolic acid-N-methylanilide.
 17. The compound of claim 1 which is 0-(methylaminosulfonyl)-glycolic acid-N-methylanilide.
 18. The compound of claim 1 which is 0-(ethylaminosulfonyl)-glycolic acid-N-methylanilide.
 19. The compound of claim 1 which is 0-(n-propylaminosulfonyl)-glycolic acid-N-methylanilide.
 20. The compound of claim 1 which is 0-(isopropylaminosulfonyl)-glycolic acid-N-methylanilide.
 21. The compound of claim 1 which is 0-(butylaminosulfonyl)-glycolic acid-N-methylanilide.
 22. The compound of claim 1 which is 0-(sec-butylaminosulfonyl)-glycolic acid-N-methylanilide.
 23. The compound of claim 1 which is 0-(aminosulfonyl)-glycolic acid-N-ethylanilide.
 24. The compound of claim 1 which is 0-(methylaminosulfonyl)-glycolic acid-N-ethylanilide.
 25. The compound of claim 1 which is 0-(ethylaminosulfonyl)-glycolic acid-N-ethylanilide.
 26. The compound of claim 1 which is 0-(n-propylaminosulfonyl)-glycolic acid-N-ethylanilide.
 27. The compound of claim 1 which is 0-(isopropylaminosulfonyl)-glycolic acid-N-ethylanilide.
 28. The compound of claim 1 which is 0-(aminosulfonyl)-glycolic acid-N-propylanilide.
 29. The compound of claim 1 which is 0-(methylaminosulfonyl)-glycolic acid-N-n-propylanilide.
 30. The compound of claim 1 which is 0-(ethylaminosulfonyl)-glycolic acid-N-n-propylanilide.
 31. The compound of claim 1 which is 0-(n-propylaminosulfonyl)-glycolic acid-N-n-propylanilide.
 32. The compound of claim 1 which is 0-(isopropylaminosulfonyl)-glycolic acid-N-n-propylanilide.
 33. The compound of claim 1 which is 0-(aminosulfonyl)-glycolic acid-N-sec-butylanilide.
 34. The compound of claim 1 which is 0-(methylaminosulfonyl)-glycolic acid-N-sec-butylanilide.
 35. The compound of claim 1 which is 0-(ethylaminosulfonyl)-glycolic acid-N-sec-butylanilide.
 36. The compound of claim 1 which is 0-(isopropylaminosulfonyl)-glycolic acid-N-secbutylanilide.
 37. The compound of claim 1 which is 0-(propylaminosulfonyl)-glycolic acid-N-sec-butylanilide.
 38. The compound of claim 1 which is 0-aminosulfonyl)-glycolic acid-N-isobutylanilide.
 39. The compound of claim 1 which is 0-(methylaminosulfonyl)-glycolic acid-N-isobutylanilide.
 40. The compound of claim 1 which is 0-(ethylaminosulfonyl)-glycolic acid-N-isobutylanilide.
 41. The compound of claim 1 which is 0-(propylaminosulfonyl)-glycolic acid-N-isobutylanilide.
 42. The compound of claim 1 which is 0-(isopropylaminosulfonyl)-glycolic acid-N-isobutylanilide. 